CN102924608B - Method for preparing wood fiber type biomass low-degradation acetylated product - Google Patents
Method for preparing wood fiber type biomass low-degradation acetylated product Download PDFInfo
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- CN102924608B CN102924608B CN201210501520.1A CN201210501520A CN102924608B CN 102924608 B CN102924608 B CN 102924608B CN 201210501520 A CN201210501520 A CN 201210501520A CN 102924608 B CN102924608 B CN 102924608B
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Abstract
The invention discloses a method for preparing a wood fiber type biomass low-degradation acetylated product. Under a mild reaction condition, low-degradation acetylation modification is carried out on the components by using a multi-step method. The method comprises the steps of peeling, grinding and drying a wood fiber raw material and carrying out acetylation modification on the raw material under a mild reaction condition, carrying out liquid-solid separation on the product after the reaction, adding water in the upper liquid to obtain a precipitate, reacting the lower solid in a reaction kettle, processing according to the operations after the reaction, carrying out a plurality of reactions on the lower solid obtained in each step, collecting the precipitate obtained in each step, and washing and drying to obtain the acetylated product. The method is mild in acetylation modification condition, so that the degradation of the product is decreased and the toxicity and the pollution level of the reaction reagents are low; and the obtained product has relatively good environmental friendliness, thermal stability and thermal plasticity, is easy to be dissolved in organic solvents and has significance in preparing thermoplastic high-polymer structural materials or functional materials via the modification of wood fibers.
Description
Technical field
The invention belongs to wood fiber biomass resource reutilization field, be specifically related to the method for a kind of lignocellulose raw material for the preparation of synthesising biological sill low degraded acetylize product.
Background technology
Along with the pay attention to day by day of the day by day exhausted of the Nonrenewable resources such as coal, oil, Sweet natural gas and various countries' environmental pollution, by rich reserves and reproducible biomass resource is converted into the focus that new forms of energy, novel material and Chemicals have become countries in the world research.The main ingredient of wood fiber biomass is Mierocrystalline cellulose, hemicellulose and xylogen, and these three kinds of main ingredients are carried out chemical modification simultaneously, is one of the important channel of efficiency utilization wood fiber biomass especially agriculture and forestry organic waste material.
At present, cellulosic modified-reaction is mainly used for reference, as esterification, etherificate, grafting etc. to the chemical modification method of wood fibre.But wood fibre is mainly with the three kinds of material associations each other of Mierocrystalline cellulose, hemicellulose and xylogen, and it has the natural high polymer of specific microcosmic and macrostructure, and the composition of its reaction mechanism and reaction product and physico-chemical property become more complicated.Therefore, to cellulosic modification, there is larger difficulty to the modification ratio of wood fibre.Remain-power English etc. adopt acetylizad method to carry out esterification modification to wood surface, and having obtained rate of body weight gain is greater than 40% and the acetylate wood that can soften near 210 DEG C; Zhang Mingqiu etc. have prepared Benzylation sisal fibers, and for the preparation of self-reinforced composite material.But this type of modification has just carried out chemical modification to lignocellulose raw material surface, its objective is the Physical Processing performance of improving xylon or the phase interface consistency with plastics compound tense, all fail to realize the efficiency utilization of each component in lignocellulose raw material.Zhou Haiyun and B.N. sarin etc. have carried out complete esterification modification to each component of lignocellulose raw material, but due to reaction conditions all comparatively violent (temperature of reaction is higher or add a large amount of trifluoroacetic acid), easily cause the degraded of product, the requirement as bio-based structured material or functional materials can not be met.
Summary of the invention
Goal of the invention: for above-mentioned problems of the prior art; the object of this invention is to provide a kind of method preparing wood fiber biomass low degraded acetylize product; multistep processes is adopted to carry out acetylization reaction to raw material under mild conditions; to obtain the acetylize product (being mainly acetylation of cellulose, hemicellulose and xylogen) of low degraded; it dissolves in common organic solvents and has higher thermostability and good thermoplasticity, can be used as the raw material preparing thermal plastic high polymer structured material or functional materials.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is as follows:
Prepare a method for wood fiber biomass low degraded acetylize product, comprise the following steps:
(1) lignocellulose raw material pulverized, dry, obtain raw material, add reactor;
(2) add acetylation reagent: with the mass ratio of raw material be 0.06 ~ 0.18 the vitriol oil, be the diacetyl oxide of 7 ~ 15 with the mass ratio of raw material and be the glacial acetic acid of 4 ~ 16 with the mass ratio of raw material, 40 ~ 120 DEG C, reaction 0.5 ~ 5h, solid-liquid separation, obtains solid and upper liquid;
(3) gained solid is carried out to the acetylize operation of repeating step (2); Wherein, the consumption of acetylation reagent is 70 ~ 90% of previous step consumption, obtains upper liquid;
(4) in upper liquid, add enough distilled water, separate out acetylize crude product, washing, to neutral post-drying, is acetylize product.
In step (1), wood fiber biomass is the mixing of one or more in Wheat Straw, Japan's branch, bagasse, maize straw and Pericarppium arachidis hypogaeae etc.
In step (2), the consumption of the vitriol oil, diacetyl oxide and glacial acetic acid, is preferably respectively 0.08% ~ 0.14, and 8 ~ 14 and 6 ~ 14.
In step (2), temperature of reaction is 60 DEG C ~ 100 DEG C, and the reaction times is 2 ~ 4h.
In step (3), reaction is 2 ~ 4 times for several times.
Beneficial effect: compared with prior art, the advantage that the present invention possesses comprises:
(1) acetylize modified condition gentleness (40 ~ 120 DEG C), and have employed multistep acetylation method, product is isolated reaction system in time, decreases the degraded of product, improve the limiting viscosity of acetylize product.
(2) modification simultaneously respectively organized by raw material; Product is dissolved in reaction medium, and can add water directly to connecing in liquid phase after solid-liquid separation, can separate out required product, feed components is fully used.
(3) product is soluble in common organic solvents, is convenient to processing.
(4) reaction reagent (vitriol oil, diacetyl oxide and glacial acetic acid) toxicity and pollution level low, products therefrom has good environment friendly, and possesses good thermostability and certain thermoplasticity.
(5) prepared by thermal plastic high polymer structured material for wood fiber biomass modification or functional materials has great importance.
Accompanying drawing explanation
Fig. 1 is the FTIR spectrum figure of wood fiber biomass low degraded acetylize modified product and raw material;
Fig. 2 is the thermal multigraph of wood fiber biomass low degraded acetylize modified product and raw material;
Fig. 3 is the differential scanning calorimetry figure of wood fiber biomass low degraded acetylize modified product and raw material.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
Embodiment 1
Pulverize oven dry by after Japan's branch peeling, cross 100 mesh sieves.Accurately take 6g Japan branch powder, move to reactor, and add acetylation reagent and comprise the vitriol oil, diacetyl oxide and glacial acetic acid, consumption (with the mass ratio of Japan's branch powder) is respectively: 8%, 12.5 and 10, stirring reaction 2h under 100 DEG C of constant temperature; Product is carried out solid-liquid separation by centrifugal mode, and lower floor's solid continues reaction in the reactor, and add the acetylation reagent that consumption is back reaction consumption 80%, temperature of reaction and time same back, product process as previously mentioned; Reaction conditions and operation are with reference to second step for the third time; Add enough distilled water (or after merging, then to add water to often walking in solid-liquid separation gained upper liquid.), the precipitate filtration washing obtained is to neutral, and oven dry is weighed, analyzed, and is finally washed to neutrality by reaction residues, and oven dry is weighed, analyzed.Result is as shown in table 1.
Table 1 efficiency of pcr product and limiting viscosity
* limiting viscosity testing method: by the acetylize product grinds powder after clean oven dry; be that solvent is dissolved with methylene dichloride; and be mixed with certain density solution, test its limiting viscosity according to GB/T 1632-93 " dilute polymer viscosity number and For Intrinsic Viscosity Measurements ".
Existing Japan branch often adopts pyroprocess and trifluoroacetic acid method to carry out acetylize, obtained acetylate, and the present embodiment carries out related experiment contrast with these two methods, specific as follows:
Raw material (the same): pulverize oven dry by after Japan's branch peeling, cross 100 mesh sieves, for subsequent use.
Pyroprocess (mainly operating): sulfuric acid, diacetyl oxide and acetic acid consumption are: 7.33%, 12 and 12, and temperature of reaction is 120 DEG C, and the reaction times is 2h.
Trifluoroacetic acid method (mainly operating): trifluoroacetic acid, perchloric acid, acetic acid and diacetyl oxide consumption difference: 2.3,6.2,1.3% and 3.2, temperature of reaction is 50 DEG C, and the reaction times is 8h.
Carry out detection to product and analyze (method is the same), result is as shown in table 2.
Products therefrom yield and limiting viscosity after table 2 wood fibre pyroprocess and the acetylize of trifluoroacetic acid method
In table 1, after acetylize, product total yield is 87.94%; lower than the yield of kind of the method products obtained therefrom of two in table 2; but its limiting viscosity is 66.28mL/g; higher than pyroprocess and trifluoroacetic acid method; show that molecular weight of product is higher; therefore, lower by the palliating degradation degree of the method for the invention to Japan's branch powder acetylize modified gained precipitation product.
Infrared spectrogram (Fig. 1) is presented at 1750 cm
-1, 1380cm
-1, 1240cm
-1there is ν respectively
c=O, δ
cH3, ν
c-O-Ccharacteristic peak, show successfully to access ethanoyl; TGA(Fig. 2) figure shows to start to decompose at 216 DEG C weightless, higher than the decomposition temperature of pyroprocess and trifluoroacetic acid products obtained therefrom, possesses better thermostability.DSC(Fig. 3) analyze show to occur second-order transition temperature at 165 DEG C to possess certain thermoplasticity; The X-ray diffraction analysis of product shows it for amorphous structure; Product dissolves in acetone; Can be used as the raw material of bio-based structured material or functional materials processing.
Embodiment 2
Pulverize oven dry by after Japan's branch peeling, cross 100 mesh sieves.Accurately take 6g raw material, move to reactor, and add acetylation reagent and comprise the vitriol oil, diacetyl oxide and glacial acetic acid, consumption (with the mass ratio of Japan's branch powder) is respectively: 12.5%, 12.5 and 10, stirring reaction 3h under 80 DEG C of constant temperature; By product by centrifugal mode solid-liquid separation, lower floor's solid transfer is to reactor, and add the acetylation reagent that consumption is back reaction consumption 80%, temperature of reaction and time same back, product process as previously mentioned; Only carry out 2 acetylizes; Add enough distilled water to often walking in solid-liquid separation gained upper liquid, the precipitate filtration washing obtained is to neutral, and oven dry is weighed, analyzed, and is finally washed to neutrality by reaction residues, and oven dry is weighed, analyzed.
Table 3 efficiency of pcr product and limiting viscosity
In table 3, acetylize product total yield is up to 111.24%; higher than the yield of kind of the method products obtained therefrom of two in table 2; its limiting viscosity is 71.09ml/g simultaneously; higher than pyroprocess and trifluoroacetic acid method; show that molecular weight of product is higher; therefore, lower by the palliating degradation degree of the method for the invention to Japan's branch powder modified gained precipitation product.
The X-ray diffraction analysis of product shows it for amorphous structure product; Infrared spectrogram is presented at 1745cm
-1, 1382cm
-1, 1240cm
-1there is ν respectively
c=O, δ
cH3, ν
c-O-Ccharacteristic peak, show successfully to access ethanoyl; Dsc analysis shows to occur second-order transition temperature at 160 DEG C, possesses certain thermoplasticity; TGA figure shows to start to decompose at 221 DEG C weightless, higher than the decomposition temperature of pyroprocess and trifluoroacetic acid products obtained therefrom, possesses better thermostability.Product dissolves in acetone.
Embodiment 3
Wheat straw is pulverized post-drying, crosses 100 mesh sieves.Accurately take 6g raw material, to reactor, and add acetylation reagent and comprise the vitriol oil, diacetyl oxide and glacial acetic acid, consumption (with the mass ratio of barley seeding food) is respectively: 12.5%, 8 and 8, stirring reaction 4h under 60 DEG C of constant temperature; By product by centrifugal mode solid-liquid separation, lower floor's solid transfer is to reactor, and add the acetylation reagent that consumption is back reaction consumption 80%, temperature of reaction and time same back, product process as previously mentioned; Only carry out 4 acetylizes; Add enough distilled water to often walking in solid-liquid separation gained upper liquid, the precipitate filtration washing obtained is to neutral, and oven dry is weighed, analyzed, and is finally washed to neutrality by reaction residues, and oven dry is weighed, analyzed.
Table 4 efficiency of pcr product and limiting viscosity
In table 4, acetylize product total yield is only 59.64%, far below the product yield of pyroprocess and trifluoroacetic acid method, shows that ethanoyl replaces efficiency lower; Reaction times is more; And its limiting viscosity is 77.82ml/g, higher than pyroprocess and trifluoroacetic acid method, show that molecular weight of product is higher, therefore, the palliating degradation degree of separating out product to the modified gained of wheat straw powder acetylize by the method for the invention is lower.
The X-ray diffraction analysis of product shows it for amorphous structure; Infrared spectrogram is presented at 1745cm
-1, 1382cm
-1, 1240cm
-1there is ν respectively
c=O, δ
cH3, ν
c-O-Ccharacteristic peak, show successfully to access ethanoyl; Dsc analysis shows to occur second-order transition temperature at 167 DEG C, possesses certain thermoplasticity; TGA figure shows to start to decompose at 240 DEG C weightless, higher than the decomposition temperature of pyroprocess and trifluoroacetic acid products obtained therefrom, possesses better thermostability.Product dissolves in acetone.Can be used as the raw material of bio-based structured material or functional materials processing.
Embodiment 4
By corn straw smashing post-drying, cross 100 mesh sieves.Accurately take 6g raw material, move to reactor, and add acetylation reagent and comprise the vitriol oil, diacetyl oxide and glacial acetic acid, consumption (with the mass ratio of raw material) is respectively: 14%, 14 and 14, stirring reaction 4h under 120 DEG C of constant temperature; By product by centrifugal mode solid-liquid separation, lower floor's solid transfer is to reactor, and add the acetylation reagent that consumption is back reaction consumption 80%, temperature of reaction and time same back, product process as previously mentioned; Only carry out 2 acetylizes; Add enough distilled water to often walking in solid-liquid separation gained upper liquid, the precipitate filtration washing obtained is to neutral, and oven dry is weighed, analyzed, and is finally washed to neutrality by reaction residues, and oven dry is weighed, analyzed.
Table 5 efficiency of pcr product and limiting viscosity
In table 5, acetylize product total yield is only 68.41%, lower than the product yield of pyroprocess and trifluoroacetic acid method; And its limiting viscosity is 62.48ml/g, higher than pyroprocess and trifluoroacetic acid method, show that molecular weight of product is higher, therefore, the palliating degradation degree of separating out product to the modified gained of corn stalk powder acetylize by the method for the invention is lower.
Infrared spectrogram is presented at 1751 cm-1,1390 cm-1,1238 cm-1 occur ν respectively
c=O, δ
cH3, ν
c-O-Ccharacteristic peak, show successfully to access ethanoyl; Dsc analysis shows to occur second-order transition temperature at 160 DEG C, possesses certain thermoplasticity; TGA figure shows to start to decompose at 200 DEG C weightless, higher than the decomposition temperature of pyroprocess and trifluoroacetic acid products obtained therefrom, possesses better thermostability.Product dissolves in acetone.Can be used as the raw material of bio-based structured material or functional materials processing.
Embodiment 5
By Japan's branch powder and the mixing of wheat straw waste powder equal proportion, cross 100 mesh sieves.Accurately take 6g mixing raw material, move to reactor, and add acetylation reagent and comprise the vitriol oil, diacetyl oxide and glacial acetic acid, consumption (with the mass ratio of mixing raw material) is respectively: 16%, 6 and 6, stirring reaction 3h under 70 DEG C of constant temperature; By product by centrifugal mode solid-liquid separation, lower floor's solid transfer is to reactor, and add the acetylation reagent that consumption is back reaction consumption 80%, temperature of reaction and time same back, product process as previously mentioned; Only carry out 3 acetylizes; Add enough distilled water to often walking in solid-liquid separation gained upper liquid, the precipitate filtration washing obtained is to neutral, and oven dry is weighed, analyzed, and is finally washed to neutrality by reaction residues, and oven dry is weighed, analyzed.
Table 6 efficiency of pcr product and limiting viscosity
In table 6, acetylize product total yield is only 80.35%, lower than the product yield of pyroprocess and trifluoroacetic acid method; And its limiting viscosity is 62.55ml/g, higher than pyroprocess and trifluoroacetic acid method, show that molecular weight of product is higher, therefore, the palliating degradation degree of separating out product to Japan's branch and the modified gained of wheat straw waste acetylize by the method for the invention is lower.
Infrared spectrogram is presented at 1751 cm-1,1390 cm-1,1238 cm-1 occur ν respectively
c=O, δ
cH3, ν
c-O-Ccharacteristic peak, show successfully to access ethanoyl; Dsc analysis shows to occur second-order transition temperature at 161 DEG C, possesses certain thermoplasticity; TGA figure shows to start to decompose at 202 DEG C weightless, higher than the decomposition temperature of pyroprocess and trifluoroacetic acid products obtained therefrom, possesses better thermostability.Product dissolves in acetone.Can be used as the raw material of bio-based structured material or functional materials processing.
Claims (7)
1. prepare a method for wood fiber biomass low degraded acetylize product, it is characterized in that, comprise the following steps:
(1) lignocellulose raw material pulverized, dry, obtain raw material, add reactor;
(2) add acetylation reagent: with the mass ratio of raw material be 0.06 ~ 0.18 the vitriol oil, be the diacetyl oxide of 7 ~ 15 with the mass ratio of raw material and be the glacial acetic acid of 4 ~ 16 with the mass ratio of raw material, 60 ~ 70 DEG C, reaction 0.5 ~ 5h, solid-liquid separation, obtains solid and upper liquid;
(3) gained solid is carried out to the acetylize operation of repeating step (2); Wherein, the consumption of acetylation reagent is 70 ~ 90% of previous step consumption, obtains upper liquid;
(4) in upper liquid, add enough distilled water, separate out acetylize crude product, washing, to neutral post-drying, is acetylize product.
2. prepare the method for wood fiber biomass low degraded acetylize product according to claim 1; it is characterized in that: in step (1), lignocellulose raw material is one or more mixing in Wheat Straw, Japan's branch, bagasse, maize straw and Pericarppium arachidis hypogaeae.
3. prepare the method for wood fiber biomass low degraded acetylize product according to claim 1, it is characterized in that: in step (2), the consumption of the vitriol oil, diacetyl oxide and glacial acetic acid is respectively 0.08 ~ 0.14,8 ~ 14 and 6 ~ 14.
4. prepare the method for wood fiber biomass low degraded acetylize product according to claim 1, it is characterized in that: in step (3), acetylation reagent consumption is 80% of back.
5. prepare the method for wood fiber biomass low degraded acetylize product according to claim 1, it is characterized in that: in step (3), acetylization reaction number of times is 2 ~ 4 times.
6. prepare the method for wood fiber biomass low degraded acetylize product according to claim 1, it is characterized in that: in step (4), first merge the upper liquid of each step gained, and then carry out remaining operation.
7. prepare the method for wood fiber biomass low degraded acetylize product according to claim 1; it is characterized in that: in step (4); the upper liquid of each step gained is added water precipitation product operation respectively, finally merges product and obtain the finished product.
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| CN104098765A (en) * | 2014-06-27 | 2014-10-15 | 广东威林工程塑料有限公司 | Synthesis method for biologically based transparent semi-aromatic poly-amide material |
| CN105131128A (en) * | 2015-09-24 | 2015-12-09 | 上海应用技术学院 | Method for efficiently preparing cellulose acetate through catalyzing waste biomass by organic solvents |
| CN106117566A (en) * | 2016-06-25 | 2016-11-16 | 芜湖三刀材料科技有限公司 | A kind of preparation method of modified wood powder |
| CN108058310A (en) * | 2017-12-14 | 2018-05-22 | 成都新柯力化工科技有限公司 | A kind of method that waste and old paper substrate compound package material recycling prepares lightweight packaging material |
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| CN101139400A (en) * | 2006-09-08 | 2008-03-12 | 中国科学院过程工程研究所 | method for separating straw acetylized component and preparing straw cellulose acetate |
| CN102120775A (en) * | 2010-12-06 | 2011-07-13 | 江南大学 | Acetylation thermoplastic modification method of rice straw |
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| CN101139400A (en) * | 2006-09-08 | 2008-03-12 | 中国科学院过程工程研究所 | method for separating straw acetylized component and preparing straw cellulose acetate |
| CN102120775A (en) * | 2010-12-06 | 2011-07-13 | 江南大学 | Acetylation thermoplastic modification method of rice straw |
Non-Patent Citations (1)
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| 机械活化预处理甘蔗渣制备醋酸纤维素的工艺;陈渊等;《农业工程学报》;20100930;第26卷(第9期);第374－380页 * |
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Inventor after: Hong Jianguo Inventor after: Yan Wei Inventor after: Li Xiaobao Inventor after: Ye Judi Inventor after: Chen Jianqiang Inventor after: Gao Qinwei Inventor before: Hong Jianguo Inventor before: Yan Wei Inventor before: Li Xiaobao Inventor before: Ye Judi Inventor before: Chen Jianqiang Inventor before: Gao Qinwei |
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